Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
  • C08L43/02—Homopolymers or copolymers of monomers containing phosphorus
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
  • C08L33/12—Homopolymers or copolymers of methyl methacrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K21/00—Fireproofing materials
  • C09K21/06—Organic materials
  • C09K21/12—Organic materials containing phosphorus
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K21/00—Fireproofing materials
  • C09K21/14—Macromolecular materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

• the present invention relates to an acrylic copolymer resin composition, and more particularly to an acrylic copolymer resin composition that meets all requirements in terms of flame retardancy, scratch resistance, impact resistance and transparency.
• Thermoplastic resins have lower specific gravities, better moldability and better impact resistance than glass and metal. With the recent trend toward low-priced, large-scale, lightweight electrical/electronic products, plastic articles have rapidly replaced glass and metal in many applications.
• thermoplastic resins are increasingly required to have good resistance to external impacts and scratches and good flame retardancy representing high fire resistance.
• Another requirement of thermoplastic resins is high transparency, which is advantageous in obtaining high colorability and satisfactory design effects of design colors such as gradation colors.
• scratch resistance, flame retardancy, impact resistance and transparency is improved, deterioration of the other physical properties is inevitable.
• there is a need to develop a resin composition that meets all requirements in terms of flame retardancy, scratch resistance, impact resistance and transparency.
• An aspect of the present invention is to provide an acrylic copolymer resin composition with excellent flame retardancy, scratch resistance, impact resistance and transparency.
• Another aspect of the present invention is to provide a molded article including the acrylic copolymer resin composition.
• an acrylic copolymer resin composition may include
• the phosphorus-containing acrylic copolymer may be a copolymer of monomers represented by Formula 1 and 2: wherein R 1 is -H or -(CH 2 ) n -CH 3 , n is an integer from 0 to 5, R 3 is t is an integer from 0 to 10, R 4 and R 5 are each independently -(O) p (CH 2 ) q X, p is an integer from 0 or 1, q is an integer from 0 to 5, and X comprises methyl, cyclohexyl, phenyl, methylphenyl, methylethylphenyl, propylphenyl, methoxyphenyl, cyclohexylphenyl, chlorophenyl, bromophenyl, phenylphenyl and benzylphenyl groups; and wherein R 1 is -H or -(CH 2 ) n -CH 3 , n is an integer from 0 to 5, R 2 is
• the monomer represented by Formula 1 may be included in an amount of at least 35 mol%, based on a base resin including (A) and (B).
• the monomer represented by Formula 1 may be included in an amount of 20 to 70 mol%, based on the phosphorus-containing acrylic copolymer.
• the phosphorus-containing acrylic copolymer may have a weight average molecular weight of 50,000 to 200,000 g/mol.
• the phosphorus-containing acrylic copolymer may be included in an amount of 40 to 85% by weight, based on the total weight of the base resin including (A) and (B).
• the polymethyl methacrylate may have a weight average molecular weight of 30,000 to 150,000 g/mol.
• the polymethyl methacrylate may be included in an amount of 15 to 60% by weight, based on the total weight of the base resin including (A) and (B).
• the transparent soft acrylate resin may be included in an amount of 1 to 18 parts by weight, based on 100 parts by total weight of the base resin including (A) and (B).
• the acrylic copolymer resin composition may further include a phosphorus-based flame retardant.
• the acrylic copolymer resin composition of the present invention is excellent in flame retardancy, scratch resistance, impact resistance and transparency. In addition, the acrylic copolymer resin composition of the present invention is prevented from deterioration in transmittance despite increased flame retardancy, scratch resistance and impact resistance.
• the present invention may provide an acrylic copolymer resin composition including
• the phosphorus-containing acrylic copolymer may be a copolymer of monomers represented by Formula 1 and 2: wherein R 1 is -H or -(CH 2 ) n -CH 3 , n is an integer from 0 to 5, R 3 is t is an integer from 0 to 10, R 4 and R 5 are each independently -(O) p (CH 2 ) q X, p is an integer from 0 or 1, q is an integer from 0 to 5, and X comprises methyl, cyclohexyl, phenyl, methylphenyl, methylethylphenyl, propylphenyl, methoxyphenyl, cyclohexylphenyl, chlorophenyl, bromophenyl, phenylphenyl and benzylphenyl groups; and wherein R 1 is -H or -(CH 2 ) n -CH 3 , n is an integer from 0 to 5, R 2 is -(CH
• the monomer represented by Formula 1 may be included in an amount of at least 35 mol%, preferably 35 to 50 mol%, based on the base resin including the phosphorus-containing acrylic copolymer (A) and the polymethyl methacrylate (B). Within this range, not only improved transparency, scratch resistance and impact resistance but also high flame retardancy rating can be ensured.
• the monomer represented by Formula 1 may be included in an amount of 20 to 70 mol%, preferably 30 to 55 mol%, based on the phosphorus-containing acrylic copolymer. Within this range, polymerization stability and flame retardancy can be advantageously ensured.
• the monomer represented by Formula 1 may include at least one phosphonate selected from the group consisting of, but not limited to, dimethyl(methacryloyloxymethyl)phosphonate, diethyl(methacryloyloxymethyl)phosphonate, dimethyl(acryloyloxymethyl)phosphonate, diethyl(acryloyloxymethyl)phosphonate, methylethyl(methacryloyloxymethyl)phosphonate, methylethyl(acryloyloxymethyl)phosphonate, dimethyl(methacryloyloxyethyl)phosphonate, diethyl(methacryloyloxyethyl)phosphonate, and dipropyl(methacryloyloxyethyl)phosphonate.
• phosphonate selected from the group consisting of, but not limited to, dimethyl(methacryloyloxymethyl)phosphonate, diethyl(methacryloyloxymethyl)phosphonate, dimethyl(acryloyloxy
• the monomer represented by Formula 2 may include at least one methacrylate or acrylate selected from the group consisting of, but not limited to, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, cyclohexyl methacrylate, and phenyl methacrylate.
• the phosphorus-containing acrylic copolymer may be prepared by bulk polymerization, emulsion polymerization or suspension polymerization of a mixture of the monomers represented by Formula 1 and 2. Suspension polymerization may be preferred.
• the polymerization temperature and time may be appropriately determined. For example, the polymerization may be performed at a temperature of 65 to 125 °C, preferably 70 to 120 °C, for about 2 to about 8 hours, but is not limited to these conditions.
• the monomer mixture may further include at least one additive selected from polymerization initiators, chain transfer agents, suspension stabilizers, suspension stabilization aids, flame retardants, surfactants, nucleating agents, coupling agents, fillers, plasticizers, impact-reinforcing agents, lubricants, antibacterial agents, release agents, heat stabilizers, antioxidants, light stabilizers, compatibilizers, inorganic additives, colorants, stabilizers, lubricating agents, antistatic agents, pigments, dyes, and flame-proofing agents.
• additives selected from polymerization initiators, chain transfer agents, suspension stabilizers, suspension stabilization aids, flame retardants, surfactants, nucleating agents, coupling agents, fillers, plasticizers, impact-reinforcing agents, lubricants, antibacterial agents, release agents, heat stabilizers, antioxidants, light stabilizers, compatibilizers, inorganic additives, colorants, stabilizers, lubricating agents, antistatic agents, pigments, dyes, and flame-proof
• the phosphorus-containing acrylic copolymer may have a weight average molecular weight of 50,000 to 200,000 g/mol, preferably 80,000 to 150,000 g/mol. Within this range, impact resistance is maintained and good polymerization stability can be ensured.
• the phosphorus-containing acrylic copolymer may be included in an amount of 40 to 85% by weight, preferably 65 to 85% by weight, based on the total weight of the base resin including the phosphorus-containing acrylic copolymer (A) and the polymethyl methacrylate (B). Within this range, transmittance may be maintained and flame retardancy can be advantageously ensured.
• the polymethyl methacrylate may be prepared from a methyl methacrylate monomer by a suitable polymerization process.
• the polymethyl methacrylate may have a weight average molecular weight of 30,000 to 150,000 g/mol, preferably 35,000 to 95,000 g/mol. Within this range, good transmittance, flowability and impact strength can be ensured.
• the polymethyl methacrylate may be included in an amount of 15 to 60% by weight, preferably 15 to 35% by weight, based on the total weight of the base resin including the phosphorus-containing acrylic copolymer (A) and the polymethyl methacrylate (B). Within this range, transmittance can be advantageously maintained.
• the transparent soft acrylate resin can improve the impact resistance of the mixture of the phosphorus-containing acrylic copolymer and the polymethyl methacrylate while maintaining the transparency of the mixture.
• the mixing of the polymethyl methacrylate with the phosphorus-containing acrylic copolymer leads to an increase in flame retardancy rating, impact resistance and scratch resistance but may cause a decrease in transmittance.
• the transparent soft acrylate resin can maintain the transmittance of the mixture of the phosphorus-containing acrylic copolymer and the polymethyl methacrylate.
• the transparent soft acrylate resin may have a refractive index of 1.485 to 1.51. Within this range, high transmittance can be advantageously ensured.
• the transparent soft acrylate resin may be included in an amount of 1 to 18 parts by weight, preferably 5 to 15 parts by weight, more preferably 5 to 10 parts by weight, based on 100 parts by weight of the base resin including the phosphorus-containing acrylic copolymer (A) and the polymethyl methacrylate (B). Within this range, improved impact resistance can be obtained, and flame retardancy rating and transmittance can be prevented from deterioration.
• the glass transition temperature of the transparent soft acrylate resin may be from 15 to 30 °C.
• the transparent soft acrylate resin may have a surface hardness of 70 or less, as measured on a 0.2 ⁇ 0.1 ⁇ m thick specimen using a durometer (GS-706N type A, TECLOCK).
• the transparent soft acrylate resin may have a total light transmittance of 88% or more, as evaluated on a 3 mm thick specimen in accordance with ASTM D1003.
• the transparent soft acrylate resin may have a structure in which a vinyl monomer is grafted onto an acrylic rubber core.
• the vinyl monomer may include at least one monomer selected from the group consisting of, but not limited to, aromatic vinyl monomers, cyanide vinyl monomers, (meth)acrylic monomers, styrenic monomers, acrylonitrile, styrene, and acrylate monomers.
• the transparent soft acrylate resin may have a structure in which methyl methacrylate and styrene are grafted onto a butyl acrylate rubber core, but is not limited to this structure.
• the acrylic copolymer resin composition may further include a phosphorus-based flame retardant.
• the phosphorus-based flame retardant is added to impart the resin composition with flame retardancy.
• the phosphorus-based flame retardant may be any of those known in the art, including red phosphorus, phosphonates and phosphinates.
• the phosphorus-based flame retardant may be represented by Formula 3: wherein R 4 , R 5 , R 7 and R 8 are each independently a C 6 -C 20 aryl group or a C 6 -C 20 aryl group substituted with C 1 -C 20 alkyl group, R 6 is a moiety derived from resorcinol, hydroquinol, bisphenol-A or bisphenol-S as a dialcohol, and n is an integer from 0 to 10.
• the phosphorus-based flame retardant of Formula 3 wherein n is 0 may be, for example, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, trixylyl phosphate, tri(2,4,6-trimethylphenyl)phosphate, tri(2,4-di-tert-butylphenyl)phosphate or tri(2,6-di-tert-butylphenyl)phosphate.
• the phosphorus-based flame retardant of Formula 3 wherein n is 1 may be, for example, resorcinol bis(diphenyl phosphate), hydroquinol bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate), resorcinol bis(2,6-di-tert-butylphenyl phosphate) or hydroquinol bis(2,6-dimethylphenyl phosphate).
• the phosphorus-based flame retardant of Formula 3 wherein n is 2 or greater may exist in the form of an oligomeric mixture.
• the phosphorus-based flame retardant may be represented by Formula 4: wherein each R 9 represents a substituent independently selected from C 1 -C 20 alkyl groups, C 6 -C 20 aryl groups, C 6 -C 20 aryl groups substituted with C 1 -C 20 alkyl, C 6 -C 20 aralkyl groups, C 1 -C 20 alkoxy groups, C 6 -C 20 aryloxy groups, amino groups, or hydroxyl groups, k and j are each independently an integer from 0 to 10, the C 1 -C 20 alkoxy groups or C 6 -C 20 aryloxy groups may be optionally substituted with at least one C 1 -C 20 alkyl groups, C 6 -C 20 aryl groups, amino groups or hydroxyl groups, R 10 is a moiety derived from a C 6 -C 20 dioxyaryl group or a C 6 -C 20 dioxyaryl group substituted with C 1 -C 20 alkyl, and n representing the
• the phosphorus-based flame retardant may be included in an amount of 0 to 20 parts by weight, preferably 0 to 10 parts by weight, based on 100 parts by weight of the acrylic copolymer resin composition.
• the acrylic copolymer resin composition may further include one or more additives.
• additives may include, but are not limited to, anti-drip agents, impact-reinforcing agents, antioxidants, plasticizers, heat stabilizers, light stabilizers, compatibilizers, pigments, dyes, inorganic additives, antibacterial agents, and antistatic agents.
• the resin composition of the present invention may have a flame retardancy rating of V1 or V0, as evaluated on 1/16", 1/12", 1/10" and 1/8" thick specimens in accordance with UL94.
• the resin composition of the present invention may have a total light transmittance of 85% or more, as evaluated on a 2.5 mm thick specimen in accordance with ASTM D1003.
• the resin composition of the present invention may have a scratch width of 260 ⁇ m to 290 ⁇ m, as measured on a 3.2 mm thick specimen by a ball-type scratch profile (BSP) test.
• BSP ball-type scratch profile
• the resin composition of the present invention may have an impact strength of 10 to 30 kgf.cm/cm, as measured on a 1/4" thick specimen in accordance with ASTM D-256.
• the resin composition of the present invention can be prepared by a suitable method known in the art.
• the resin composition of the present invention may be prepared in the form of pellets.
• the constituent components and optionally other additives are simultaneously mixed, melt-extruded in an extruder, and pelletized.
• the pellets may be molded into a plastic article by injection molding or extrusion molding.
• the present invention also provides a molded article produced by molding the acrylic copolymer resin composition.
• molding processes suitable for the production of the molded article include, but are not limited to, extrusion, injection molding and casting, which are widely known to those skilled in the art.
• the components were mixed in the amounts (parts by weight, based on solid content) shown in Tables 1 and 2, and then a heat stabilizer and an antioxidant were added thereto to prepare resin compositions.
• the extrudate was produced in the form of pellets.
• the pellets were processed into a 100 x 100 mm specimen for scratch resistance evaluation, 1/16", 1/12", 1/10" and 1/8" thick specimens for flame retardancy evaluation, a 1/4" thick specimen for Izod unnotched impact strength evaluation, and a 2.5 mm thick specimen for the transmittance measurement using a 10 oz injection molding machine at 200-220 °C. After standing at 23 °C and 50% relative humidity for 48 hr, the physical properties of the specimens were evaluated. The results are shown in Tables 3 and 4.
• the impact strength (kgf.cm/cm) of the specimen was measured according to ASTM D-256.
• the flame retardancy of the specimens was evaluated according to UL 94.
• the char yield (%) at 700 °C was determined by measuring the remaining amount of char at 700 °C after TGA at a heating rate of 20 °C/min under a nitrogen atmosphere, and calculating the proportion of the remaining amount relative to the initial amount of char.
• the acrylic copolymer resin compositions of Examples 1-6 showed excellent flame retardancy, scratch resistance, impact resistance and transmittance.
• the resin compositions of Examples 1-6 each including the monomer represented by Formula 1 in an amount of 35% by weight or more with respect to the weight of the base resin including (A) and (B), had better flame retardancy ratings than the resin composition of Comparative Example 1.
• the acrylic copolymer resin compositions of Examples 1-5 including the transparent soft acrylate resin had better flame retardancy ratings, scratch resistance, impact resistance and transmittances than the resin compositions of Comparative Examples 2-6.
• the use of the transparent soft acrylate resin within the content range defined in the present invention led to an improvement in the impact resistance of the resin compositions while maintaining the flame retardancy rating and transmittance of the resin compositions (see Examples 1-6 and Comparative Example 7).

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• Chemical Kinetics & Catalysis (AREA)
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• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 2010
  • 2010-12-23 KR KR1020100133980A patent/KR101411004B1/ko active IP Right Grant
  • 2010-12-29 WO PCT/KR2010/009531 patent/WO2012086867A1/fr unknown
  • 2010-12-29 JP JP2013545990A patent/JP5706540B2/ja not_active Expired - Fee Related
  • 2010-12-29 EP EP10861207.8A patent/EP2657292B1/fr not_active Not-in-force

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